EP0454326B1 - Agent dispersant anti-oxydant multifonctionnel améliorant l'index de viscosité - Google Patents

Agent dispersant anti-oxydant multifonctionnel améliorant l'index de viscosité Download PDF

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Publication number
EP0454326B1
EP0454326B1 EP91303235A EP91303235A EP0454326B1 EP 0454326 B1 EP0454326 B1 EP 0454326B1 EP 91303235 A EP91303235 A EP 91303235A EP 91303235 A EP91303235 A EP 91303235A EP 0454326 B1 EP0454326 B1 EP 0454326B1
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Prior art keywords
polymer
carbon
graft
isocyanate
ethylene
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German (de)
English (en)
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EP0454326A1 (fr
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Maria Magdalena Kapuscinski
Thomas Francis De Rosa
Robert Thomas Biggs
Theodore Eugene Nalesnik
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DSM Copolymer Inc
Texaco Development Corp
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Texaco Development Corp
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M149/00—Lubricating compositions characterised by the additive being a macromolecular compound containing nitrogen
    • C10M149/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M149/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amino group
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M149/00—Lubricating compositions characterised by the additive being a macromolecular compound containing nitrogen
    • C10M149/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M149/06—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amido or imido group
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/026—Butene
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/024—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings having at least two phenol groups but no condensed ring
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/086—Imides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28—Amides; Imides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/022—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amino group
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/024—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amido or imido group
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/06—Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts

Definitions

  • This invention relates to a multi-functional lubricant additive which is a dispersant, anti-oxidant and a V.I. improver (VIP) additive when employed in a lubricating oil composition.
  • V.I. improver V.I. improver
  • hydrocarbon lubricating oils must be formulated by addition of various additives to improve their properties.
  • U.S. 3,522,180 discloses a method for the preparation of an ethylene-propylene copolymer substrate effective as a viscosity index improver for lubricating oils.
  • U.S 4,089,794 discloses ethylene copolymers derived from ethylene and one of more (C3 to C28) alpha olefin solution grafted with an ethylenically-unsaturated carboxylic acid material followed by a reaction with a polyfunctional material reactive with carboxyl groups, such as a polyamine, a polyol, or a hydroxylamine which reaction product is useful as a sludge and varnish control additive in lubricating oils.
  • a polyfunctional material reactive with carboxyl groups such as a polyamine, a polyol, or a hydroxylamine
  • U.S. 4,137,185 discloses a stabilized imide graft of an ethylene copolymer additive for lubricants.
  • U.S. 4,146,489 discloses a graft copolymer where the backbone polymer is an oil-soluble ethylene-propylene copolymer or an ethylene-propylene-diene modified terpolymer with a graft monomer of C-vinylpyridine or N-vinylpyrrolidone to provide a dispersant VI improver for lubricating oils.
  • U.S. 4,320,019 discloses a multipurpose lubricating additive prepared by the reaction of an interpolymer of ethylene and a (C3-C8) alpha-monoolefin with an olefinic carboxylic acid acylating agent to form an acylating reaction intermediate which is then reacted with an amine.
  • U.S. 4,764,304 discloses a lubricating oil dispersant VI improver composition containing an additive prepared by the reaction of an olefin copolymer and an unsaturated isocyanate to form reactive intermediate which is then reacted with heterocyclic amines.
  • U.S. 4,340,689 discloses a process for grafting a functional organic group onto an ethylene copolymer or an ethylene-propylene-diene terpolymer.
  • U.S. 4,357,250 discloses a reaction product of a copolymer and an olefin carboxylic acid via the "ene” reaction followed by a reaction with a monoamine-polyamine mixture.
  • U.S.4,382,007 discloses a dispersant - VI improver prepared by reacting a polyamine-derived dispersant with an oxidized ethylene-propylene polymer or an ethylene-propylene diene terpolymer.
  • U.S. 4,144,181 discloses polymer additives for fuels and lubricants comprising a grafted ethylene copolymer reacted with a polyamine, polyol or hydroxyamine and finally reacted with an alkaryl sulfonic acid.
  • An object of this invention is to provide a derivatized copolymer composition.
  • Another object is to provide a process for preparing a derivatized copolymer with an unsaturated isocyanate to form a reactive intermediate which is then reacted with an antioxidant aromatic hindered amine.
  • Still another object of this invention is to provide a multi-functional lubricant additive effective for imparting viscosity index, dispersancy and anti-oxidant properties to a lubricating oil composition.
  • a further object is to provide a novel lubricating oil composition containing the copolymer additive of the invention as well as to provide concentrates of the additive of the invention.
  • the present invention is directed to a method of making dispersant/antioxidant VI improvers based on a polymer prepared in a two-step process which comprises using olefin copolymers as a polymer base derived with unsaturated isocyanates and hindered aromatic amines.
  • unsaturated isocyanate is grafted under elevated temperatures with the addition of a free radical initiator.
  • the grafting reaction is followed by a capping of a hindered aromatic amine.
  • the reaction product of the invention preferably is prepared using ethylene-propylene copolymer (EPM) or ethylene-propylene diene terpolymer (EPDM) as a polymer base, isocyanato ethyl methacrylate as a functionalizing agent and N-phenyl-p-phenylene diamine as a hindered aromatic amine.
  • EPM ethylene-propylene copolymer
  • EPDM ethylene-propylene diene terpolymer
  • the lubricant of the present invention comprises a major portion of an oil of lubricating viscosity and a minor effective amount of the reaction product.
  • the lubricating oil will be characterized by having viscosity index improver, dispersancy and anti-oxidant properties.
  • This invention as discussed briefly above, is directed to a polymer comprising an oil-soluble, substantially linear, carbon-carbon backbone polymer bearing dispersant and antioxidant units thereon, derived from a functional monomer containing a isocyanate group and an aromatic hindered amine such as N-phenyl-p-phenylene diamine.
  • the charge polymer which may be employed in the practice of the present process of this invention may include an oil-soluble, substantially linear, carbon-carbon backbone polymer.
  • R ⁇ may be divalent hydrocarbon typified alkylene, alkarylene, cycloalkylene, arylene.
  • Illustrative of such monomers may be acrylates, methacrylate, vinyl halides (such as vinyl chloride), styrene, olefins such as propylene, butylene, ; vinyl acetate; dienes such as butadiene, isoprene, hexadiene, ethylidene norbornene, Homopolymers of olefins (such as polypropylene, polybutylene, .), dienes (such as hydrogenated polyisoprene), or copolymers of ethylene, with e.g. butylene and higher olefins, styrene, isoprene and/or butadiene may be employed.
  • vinyl halides such as vinyl chloride
  • styrene olefins
  • olefins such as propylene, butylene, ; vinyl acetate
  • dienes such as butadiene, isoprene,
  • the polymer and copolymers prepared from the above mentioned monomers having short and long branches or star shape structure may also be employed.
  • the preferred carbon-carbon backbone polymers include those selected from the group consisting of ethylene-propylene copolymers (EPM or EPR) and ethylene-propylene-diene terpolymers (EPDM or EPT).
  • the charge polymer is an ethylene-propylene copolymer (EPM), it may be formed by copolymerization of ethylene and propylene under known conditions preferably Ziegler-Natta reaction conditions.
  • the preferred EPM copolymers contain units derived from the ethylene in amount of 40-90 mole %, preferably 55-80 mole %, say 60 mole %, the remainder being derived from propylene.
  • the molecular weight M ⁇ n of the EPM copolymers which may be employed may be about 10,000 to about 1,000,000, preferably about 20,000 to about 200,000, and most preferably about 140,000.
  • the molecular weight distribution may be characterized by M ⁇ w / M ⁇ n of less than about 15, preferably 1.2-10, say 1.8.
  • EPM copolymers which may be employed in practice of the process of this invention may be those set forth below in Table I, the first listed being preferred.
  • the charge polymer is ethylene-propylene-diene terpolymer (EPT or EPDM), it may be formed by copolymerization of ethylene, propylene, and diene monomers.
  • the diene monomer is commonly a non-conjugated diene typified by dicyclopentadiene; 1.4-hexadiene; ethylidene norbornene or vinyl norbornene. Polymerization is effected under known conditions generally comparable to those employed in preparing the EPM products.
  • the preferred terpolymers contain units derived from ethylene in amount of 40-70 mole %, preferably 50-65 mole mole %, say 60 mole % and units derived from propylene in an amount of 20-60 mole%, preferably 30-50 mole %, say 38 mole % and units derived from diene third monomer in amount of 0.5-15 mole %, preferably 1-10 mole %, say 2 mole %.
  • the molecular weight M ⁇ n of the terpolymers may typically be about 10,000 to about 500,000, preferably about 20,000 to about 200,000, and most preferably about 120,000.
  • Molecular weight distribution of the useful polymers is preferably narrow with a M ⁇ w / M ⁇ n of typically less than 10, preferably 1.5-5, say about 2.2.
  • EPT terpolymers which may be employed in the practice of the present process may be those set forth below in Table II, the first listed being preferred.
  • the additive is prepared in a two-step process.
  • a functional monomer containing isocyanate group is grafted in the presence of a free radical initiator.
  • a hindered aromatic amine is reacted with the pendant isocyanate groups of the said polymer.
  • the graft functional monomers which may be employed may be characterized by the presence of units containing an ethylenically unsaturated carbon-carbon double bond and an isocyanate group.
  • the graft monomer may contain more than one ethylenically unsaturated carbon-carbon double bond or isocyanate group in a preferred embodiment it may contain one of each. Graft monomers containing more than one ethylenically unsaturated carbon-carbon double bond are much less preferred because of the high probability of cross-linking during subsequent reaction.
  • the preferred graft functional monomer maybe characterized by the formula
  • R" may be a hydrocarbon group selected from the group consisting of alkylene, aralkylene, cycloalkylene, arylene, and alkarylene, including such radicals when inertly substituted.
  • R" is alkylene, it may typically be methylene, ethylene, n-propylene, iso-propylene, n-butylene, i-butylene, sec-butylene, amylene, octylene, decylene, octadecylene.
  • R" is aralkylene, it may typically be benzylene, betaphenylethylene.
  • R" When R" is cycloalkylene it may typically be cyclohexylene, cycloheptylene, cyclooctylene, 2-methylcycloheptylene, 3-butylcyclohexylene, 3-methycyclohexylene.
  • R" When R" is arylene, it may typically be phenylene, naphthylene.
  • R" When R" is alkarylene, it may typically be tolylene, xylylene.
  • R" may be inertly substituted , i.e., it may bear a non-reactive substituent such as alkyl, aryl, cycloalky, ether,
  • R ⁇ may preferably be ethylene - CH2 CH2 -.
  • R may be hydrogen or a hydrocarbon selected from the group consisting of alkyl, aralkyl, cycloalkyl, aryl, and alkaryl, including such radicals when inertly substituted.
  • R When R is alkyl, it may typically be methyl, ethyl, n-propyl, iso-propyl, n-butyl, i-butyl, sec-buty, amyl, octyl, decyl, octadecyl.
  • R when R is aralkyl, it may typically be benzyl, beta-phenylethyl.
  • R When R is cycloalkyl, it may typically be cyclohexyl, cyloheptyo, cyclooctyl, 2-methylcycloheptyl, 3-butylcyclohexyl, 3-methylcyclohexyl.
  • R When R is aryl, it may typically be phenyl, naphthyl.
  • R When R is alkaryl, it may typically be tolyl, xylol.
  • R may be inertly substituted i.e. it may bear a non-reactive substituent such as alkyl, aryl, cycloalkyl, ether.
  • R groups may include 2-ethoxyethyl, carboethoxymethyl, 4-methyl cyclohexyl.
  • the preferred R groups may be lower alkyl, i.e. C1-C10 alkyl, groups including eg methyl, ethyl, n-propyl, i-propyl, butyls, amyls, hexyls, octyls, decyls.
  • R may preferably be methyl.
  • the graft functional monomer may be an isocyanate of an unsaturated hydrocarbon typified by those hydrocarbons listed below in Table III: TABLE III allyl isocyanate buten-2-yl isocyanate buten-3-yl isocyanate p-isocyanato styrene 2,6-diisocyanato styrene m-isopropenyl-a,a-dimethyl-benzyl isocyanate
  • the functional monomer may be an isocyanate of an unsaturated acid (as acid or as ester) typified by: 4-isocyanato-butene-2-carboxylic acid
  • the preferred graft functional monomers may be isocyanatohydrocarbyl esters of unsaturated monocarboxylic acids, typified by those esters listed below in Table IV: Table IV Isocyanatoethyl methacrylate Isocyanatomethyl acrylate Omegaoisocyanato-n-butyl methacrylate
  • the preferred graft functional monomer may be isocyanatoethyl methacrylate.
  • the graft functional monomers may be grafted onto carbon-carbon backbone polymers.
  • diluent-solvent may be a hydrocarbon solvent such as mineral oil, n-hexane, n-heptane, or tetrahydrofuran.
  • Preferred solvent may be a commercial hexane containing principally hexane isomers or a commercial mineral grafting oil.
  • Reaction mixture may then be heated under nitrogen to reaction conditions of 60°C-180°C, preferably 150°C-170°C, say 155°C.
  • reaction is carried out in pressure reactor at 15-300 psig, preferably 180-220 psig, say 200 psig. (1-21 x 103 Pa, preferably 12-15 x 103 Pa, say 14 x 103 Pa at gauge).
  • Graft monomer typically isocyanoethyl methacrylate
  • Typical free radical initiators may include dicumyl peroxide, di-t-butyl peroxide, benzoyl peroxide, di-isopropyl peroxide, azobisisobutyronitrile, etc.
  • the solvent is preferably the same as that in which the EPM or EPT is dissolved.
  • the initiator may be added in amount of 0.2-40 parts, say 2 part in 0.8-120 parts, say 2 parts.
  • the preferred free radical initiator is a dicumyl peroxide (DICUP).
  • the reaction is carried out at a temperature at least as high as the decomposition temperature of the initiator, typically 60°C or higher.
  • the grafting reaction is typically carried out at graft polymerization conditions of 60°C-180°C, say 155°C during which time bonding of the graft functional monomer onto the base EPM or EPT polymer occurs.
  • reaction may proceed as follows:
  • the product graft polymer may be characterized by the presence of pendant isocyanato groups -NCO bonded to the polymer backbone thorough the residue of the graft monomer, the latter being bonded to the polymer backbone through one of the carbon atoms which formed the ethylenically unsaturated double bond.
  • the graft product polymer may contain 0.1-20, say 0.4 units derived from graft monomer per 1000 carbon atoms of the charge backbone polymer.
  • the graft polymer bearing pendant isocyanate groups may be reacted with an aromatic amine containing at least one non-tertiary nitrogen atom.
  • the amine may be characterized by the formula R* R** NH.
  • R** represents hydrogen or an organic radical having from 1 to 10 carbon atoms which may contain nitrogen, oxygen or sulfur atoms.
  • R** preferably represents hydrogen or an alkyl, alkaryl, aralkyl, cycloalkyl or aryl group.
  • R* represents an aromatic hindered amine. It is preferred that the amine be a N-phenyl-p-phenylene diamine.
  • Amidization may be carried out by adding the graft polymer containing isocyanate groups to a reaction vessel together with inert-diluent solvent.
  • reaction may be carried out in the same solvent and in the same reaction medium as that in which the polymer is dissolved.
  • reaction may proceed as follows:
  • An amine typically N-phenyl-p-phenylene diamine is added to the reaction vessel.
  • the amount of amine added is preferably 0.1-5 moles, say 1.2 moles per mole of isocyanate group bonded to the polymer. Typically this may correspond to 0.01 - 0.5 moles, say -.039 moles of amine per 100g of polymer.
  • the amidization reaction is carried out over 0.1 - 10 hours, say 2 hours at 100°C-180°C, say 155°C with agitation.
  • the final produced may be diluted to form a solution of 4 - 20 parts, say 13 parts of polymer in 80-95, say 87 parts of mineral oil such as a SUS 100 oil typified by SNO-100.
  • mineral oil such as a SUS 100 oil typified by SNO-100.
  • the fluid solution (a lubricating additive) is used for further testing.
  • the so-prepared polymer solution in oil may find use in lubricating oils as multifunctional additive (e.g. dispersant viscosity) index improvers which provide anti-oxidant properties, etc) when present in effective amount of about 1.0 to about 20 wt%, preferably 3-15 wt%, preferably about 0.9 wt%.
  • multifunctional additive e.g. dispersant viscosity index improvers which provide anti-oxidant properties, etc
  • Lubricating oils in which the multifunctional additives of this invention may find use may include automotive, aircraft, marine, railway, oils; oils used in spark ignition or compression ignition; summer or winter oils.
  • the lubricating oils may be characterized by a b.p. of about 570°F to about 660°F (300-350°C) preferably 610°F (320°C) an e.p. of about 750°F to about 1200°F (400-650°C) preferably 1020°F (550°C) and an API gravity of about 25 to about 31, preferably about 29.
  • a typical lubricating oil in which the polymer of this invention may be present may be a standard SAE 5W-30 hydrocarbon motor oil formulation having the composition as set forth below in Table V: TABLE V Wt % Base Oil 82 - Viscosity Index Improver (additive of this invention) 9 (10 w% ethylene-propylene copolymer in 90% inert oil) - Standard Additive Package: 9 Polyisobutenyl (M1290) n succinimide (dispersant); calcium sulfonate (detergent); Zinc dithiophosphate (anti-wear); di-nonyl diphenyl amine (anti-oxidant); 4,4'-methylene-bis (2,6-di-butyl phenol) (antioxidant)
  • the present invention comprises making dispersant and antioxidant VI improvers by derivatizing hydrocarbon polymers such as ethylene-propylene copolymer (EPM), or ethylene-propylene-diene terpolymer (EPDM) with, e.g., isocyanate ethyl methacryate and a hindered aromatic amine such as N-phenyl-p-phenylene diamine.
  • hydrocarbon polymers such as ethylene-propylene copolymer (EPM), or ethylene-propylene-diene terpolymer (EPDM)
  • EPM ethylene-propylene copolymer
  • EPDM ethylene-propylene-diene terpolymer
  • Addition of the above invention additives, to a lubricating oil, may be facilitated by use of a concentrate containing 0.2 to 20 wt.%, preferably 1 to 20 wt%, most preferably 4 to 14 wt%, of polymer.
  • the grafting yield of a grafted monomer is usually determined by IR-analysis of isolated rubber. Changes in the aromatic band at 1600 CM-1 compared to the ungrafted rubber band at 722 cm-1 are examined.
  • the rubber is isolated from solution by multiple dissolvation/precipitation using cyclohexane as a solvent and acetone as precipitator. Then the rubber is dried in vacuum at 60°C for 36 hours.
  • an OCP is modified by grafting isocyanato ethyl methacrylate (IEM) and capping N-phenyl-p-phenylenediamine (NPPDA).
  • the isocyanato ethylmethacrylate is grafted onto EPM containing around 0.3 mole% of ethylidene norbornene (extruded EPsyn 4106) in presence of free radical initiator, dicumyl peroxide.
  • an OCP is modified by grafting m-isopropenyl-a,a-dimethyl-benzyl isocyanate (TMI) and capping N-phenyl-p-phenylenediamine (NPPDA).
  • TMI m-isopropenyl-a,a-dimethyl-benzyl isocyanate
  • NPPDA N-phenyl-p-phenylenediamine
  • EPM solution in mineral oil 12.5 wt% EPM solution in mineral oil is prepared. 100 wt parts of EPM which is used in the example 1, is added to 400 wt parts of SUN-148 and 300 wt parts of SNO-100. The mixture is heated to 155°C with stirring and under nitrogen for 3 hours until the rubber is completely dissolved.

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  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Claims (12)

  1. Polymère greffé substantiellement linéaire ayant un squelette carbone-carbone qui comprend un polymère squelette carbone-carbone substantiellement linéaire et, polymérisé par greffage sur celui-ci, dans des conditions de réaction de polymérisation par greffage en présence d'un initiateur de radicaux libres, un monomère greffé contenant une double liaison carbone-carbone éthyléniquement insaturée et un groupe isocyanate qui a été amidé par réaction avec une amine aromatique empêchée contenant un atome d'azote non tertiaire dans le groupe amino.
  2. Polymère selon la revendication 1, dans lequel ledit polymère squelette est un copolymère d'éthylène-propylène ou un terpolymère éthylène-propylène-diène.
  3. Polymère selon la revendication 1 ou la revendication 2, dans lequel ledit monomère greffé contient le groupe
    Figure imgb0036
     où R est un hydrogène ou un groupe hydrocarboné alkyle, alcaryle, aralkyle, cycloalkyle ou aryle, et R" est un groupe hydrocarboné alkylène, aralkylène, alcarylène, cycloalkylène ou arylène.
  4. Polymère selon la revendication 3, dans lequel ledit monomère greffé est le méthacrylate d'isocyanatoéthyle, l'isocyanate d'allyle, l'isocyanate de butène-2-yle, l'isocyanate de butène-3-yle, le p-isocyanate styrène, le 2,6-diisocyanato styrène ou l'isocyanate de m-isoprényl-a,a-diméthylbenzyle.
  5. Polymère selon l'une quelconque des revendications 1 à 4, dans lequel ladite amine est R*R**NH où R** est de l'hydrogène ou un groupe alkyle, alcaryle, aralkyle, cycloalkyle ou aryle, et R* est une amine aromatique empêchée.
  6. Polymère selon la revendication 5, dans lequel ladite amine est la N-phényl-p-phénylènediamine.
  7. Procédé de préparation d'une composition de polymère substantiellement linéaire contenant un squelette carbone-carbone, qui comprend : la formation d'un mélange réactionnel contenant un polymère squelette carbone-carbone substantiellement linéaire ; la polymérisation par greffage sur ledit polymère squelette carbone-carbone substantiellement linéaire, en présence d'un initiateur de radicaux libres, d'un monomère greffé contenant une double liaison carbone-carbone éthyléniquement insaturée et un groupe isocyanate, formant ainsi un polymère greffé portant un groupe isocyanate pendant ; l'amidation dudit polymère greffé portant un groupe isocyanate pendant avec une amine aromatique empêchée contenant un atome d'azote non tertiaire dans le groupe amino, convertissant ainsi ledit groupe isocyanate en un groupe urée pendant sur ladite composition de polymère et formant un polymère greffé contenant un groupe urée pendant.
  8. Procédé de préparation d'une composition selon la revendication 7, dans lequel ledit polymère squelette est un copolymère d'éthylène-propylène ou un terpolymère d'éthylène-propylène-diène.
  9. Procédé de préparation d'une composition selon la revendication 7 ou la revendication 8, dans lequel ledit monomère greffé est le méthacrylate d'isocyanatoéthyle, l'isocyanate d'allyle, l'isocyanate de butène-2-yle, l'isocyanate de butène-3-yle, le p-isocyanato styrène, le 2,6-diisocyanato styrène, ou l'isocyanate de m-isoprényl-a,a-diméthylbenzyle.
  10. Procédé de préparation d'une composition selon l'une quelconque des revendications 7 à 9, dans lequel l'amine est la N-phényl-p-phénylènediamine.
  11. Composition d'huile lubrifiante comprenant une partie majeure d'huile lubrifiante et une partie mineure efficace, améliorant l'indice de viscosité, d'un polymère tel que revendiqué dans l'une quelconque des revendications 1 à 6.
  12. Composition d'huile lubrifiante selon la revendication 11, dans laquelle ladite partie mineure efficace améliorant l'indice de viscosité est 0,2 à 20 % en poids.
EP91303235A 1990-04-23 1991-04-11 Agent dispersant anti-oxydant multifonctionnel améliorant l'index de viscosité Expired - Lifetime EP0454326B1 (fr)

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US07/513,374 US5021177A (en) 1990-04-23 1990-04-23 Dispersant-antioxidant multifunctional viscosity index improver

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CA2036862A1 (fr) * 1990-02-23 1991-08-24 Tony L. Caines Procede en continu pour l'obtention de solutions de produits d'addition d'epm ou d'epdm dans l'huile
US5135671A (en) * 1991-04-24 1992-08-04 Texaco Inc. Multifunctional viscosity index improver containing units from unsaturated chlorides and aromatic amines
CA2394823A1 (fr) * 1999-12-30 2001-07-12 Uniroyal Chemical Company, Inc. Amines anti-oxydantes a base de n-(4-anilinophenyl)amides
US6632880B2 (en) * 2001-07-09 2003-10-14 E. I. Du Pont De Nemours And Company Coating compositions containing isocyanate-functional non-aqueous dispersed polymers
US7375061B2 (en) * 2004-09-08 2008-05-20 Crompton Corporation Antioxidant hydrazides and derivatives thereof having multifunctional activity
CN104194868A (zh) * 2014-09-16 2014-12-10 吉林化工学院 一种耐低温型粘度指数改进剂及其制备方法
CN112724312B (zh) * 2020-12-31 2021-10-08 中国科学院兰州化学物理研究所 一种脲基聚合物凝胶因子及其制备方法和凝胶润滑剂及其制备方法和应用

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US3687905A (en) * 1970-03-16 1972-08-29 Lubrizol Corp Reaction product of carboxylic acid with degraded ethylene-propylene interpolymer
US4316967A (en) * 1975-05-05 1982-02-23 The Firestone Tire & Rubber Company Amine terminated polymers and the formation of block copolymers
US4051050A (en) * 1976-04-26 1977-09-27 Exxon Research & Engineering Co. Oil-soluble anionic-graft polymer of ethylene-propylene copolymer and anionically polymerizable monomer having utility as multifunctional V. I. improver for lubricating oils
CA1159465A (fr) * 1979-09-12 1983-12-27 Won R. Song Additifs pour hydrocarbures renfermant du thiocarbamyle
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US4764304A (en) * 1986-09-25 1988-08-16 Texaco Inc. Hydrocarbon compositions containing polyolefin graft polymers

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US5021177A (en) 1991-06-04
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EP0454326A1 (fr) 1991-10-30

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